CN108178177B - A kind of preparation method of low agglomeration nano calcium carbonate - Google Patents

A kind of preparation method of low agglomeration nano calcium carbonate Download PDF

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CN108178177B
CN108178177B CN201810190909.6A CN201810190909A CN108178177B CN 108178177 B CN108178177 B CN 108178177B CN 201810190909 A CN201810190909 A CN 201810190909A CN 108178177 B CN108178177 B CN 108178177B
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calcium carbonate
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CN108178177A (en
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蒋央芳
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Guangxi Xingye Shitai Nano Technology Co.,Ltd.
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/18Carbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/02Oxides or hydroxides
    • C01F11/04Oxides or hydroxides by thermal decomposition
    • C01F11/06Oxides or hydroxides by thermal decomposition of carbonates
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    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
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    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The present invention discloses a kind of preparation method of low agglomeration nano calcium carbonate.Pretreatment, water is added in calcium sulfate and carries out pulp, then ammonium bicarbonate soln is added, reacts 0.5-1 hours, then carries out secondary filter, by filtrate temperature reaction, then filter, air-flow after residue washing, drying be crushed, then temperature be 650-750 DEG C calcining 1-2 hours, then it is sieved after air-flow is broken, obtains lime powder;Lime powder is added in the container equipped with supercritical carbon dioxide, while then additional ultrasound, ultrasonic time 60-120min start to release stress, while container being connected to dust arrester installation, collects solid to get low agglomeration nano calcium carbonate is arrived.Present invention process is simple, at low cost, and obtained nanometer calcium carbonate, good dispersion, reunion index is low, purity is high, and impurity content is low.

Description

A kind of preparation method of low agglomeration nano calcium carbonate
Technical field
The present invention relates to a kind of preparation methods of low agglomeration nano calcium carbonate, belong to field of nanometer material technology.
Background technique
It is more than critical pressure (Pc) and critical-temperature (Tc) by pressure locating for certain fluid (P) and temperature (T) in engineering When this state it is referred to as overcritical.
As the temperature and pressure of environment changes, all there are three kinds of phase-gas phases in any substance, liquid phase, solid phase, and three The point that the equilibrium state that coordinates coexists is three phase point liquid, and state point that gas two-phase phase interface disappears is super critical point in critical point Temperature and pressure is known as critical-temperature and critical pressure, and the pressure and temperature of different its critical point of substance is different.It is super to face Boundary's fluid (SuperCriticalfluid, abbreviation SCF) refers to that temperature and pressure is above the fluid of its critical point, is commonly used to make It is standby at supercritical fluid have carbon dioxide, ammonia, ethylene, propane, propylene, water etc..When object is in a supercritical state, due to gas Liquid two-phase property is very close, distinguishes so that can not understand, so being referred to as " supercritical fluid ".
Supercritical fluid has the similar diffusivity of gas and the solvability of liquid, while having both low-viscosity, low surface The characteristic of tension, the substance for enabling supercritical fluid to quickly penetrate into micropore are accordingly used in extraction rate when extraction Quicker and effective than liquid, especially solvability can change with temperature, pressure and polarity.
Nanometer calcium carbonate is a kind of Novel super-thin solid material to grow up the 1980s.It is with nonmetallic Ore lime stone is raw material, using the important inorganic salts new product of precipitation method synthetising nanometre powder body technique preparation.Its partial size 1~ Between 100nm.Partial size is small, and it is a kind of novel high-grade functional inorganic material that activity is good.
Conventional liquid phase method synthesis has that the reunion of nanometer calcium carbonate is serious, general reunion index meeting > 15, and Preparation method is complicated, generates a large amount of sewage and at high cost.
Summary of the invention
In view of this, the present invention provides a kind of preparation method of low agglomeration nano calcium carbonate, simple process and low cost, Obtained nanometer calcium carbonate, good dispersion, reunion index is low, purity is high, and impurity content is low.
The present invention solves above-mentioned technical problem by following technological means:
A kind of preparation method of low agglomeration nano calcium carbonate, is following steps:
(1) it pre-processes, water is added in calcium sulfate and carries out pulp, be then 15-35 DEG C of addition ammonium bicarbonate soln in temperature, It is 20-35 DEG C in temperature, pH is that 7.0-7.3 reacts 0.5-1 hours, then carries out secondary filter, filtrate, which is warming up to temperature, is It 80-90 DEG C, reacts 2-4 hours, then filters, air-flow after residue washing, drying is crushed, be then 650-750 DEG C in temperature Then calcining 1-2 hours crosses 300-350 mesh after air-flow is broken, obtains lime powder;
(2) lime powder for obtaining step (1) is added in the container equipped with supercritical carbon dioxide, and maintenance temperature is 45-55 DEG C, pressure is 75-80 atmospheric pressure, while then additional ultrasound, ultrasonic time 60-120min start to release stress, Container is connected to dust arrester installation simultaneously, collects solid to get low agglomeration nano calcium carbonate is arrived.
Calcium sulfate is technical grade purity in the step (1), and content of magnesium is lower than 100ppm, other metal impurities in calcium sulfate Content is lower than 50ppm, and granularity is less than 50 microns, and the mass ratio of calcium sulfate and water is 1:5-6 when pulp, ammonium bicarbonate soln it is dense Degree is 100-150g/L, and the molar ratio of the ammonium hydrogen carbonate of addition and calcium sulfate is 2.5-2.8:1, be added ammonium bicarbonate soln when Between be 1-2 hour, secondary filter uses ceramic filtration membrane, and the aperture of ceramic filtration membrane is 20-50nm.
The molar ratio of lime powder and supercritical carbon dioxide is 1:5-10 in the step (2), and ultrasonic power is 2-5kW, container inside lining polytetrafluoroethylene (PTFE) material, dust arrester installation include that two-stage is gathered dust, and the first order is cyclone dust collector, the second level For bagroom, for the cloth bag that bag collection uses for 1000-1200 mesh, cyclone dust collection material and bag collection material carry out mixing.
Container is connected to dust arrester installation by pipeline in the step (2), and ball valve is provided on pipeline, releases stress process For ball valve is opened.
The present invention uses the calcium sulfate by technical grade, reacts to obtain calcium bicarbonate by ammonium hydrogen carbonate, then carry out Filter, part beavy metal impurity can be removed, then again temperature be 80-90 DEG C, react 2-4 hours, then filter, filter residue taken to pass through Washing, available calcium carbonate are crossed, to realize the removal of part magnesium in calcium, to improve the purity of calcium oxide, reduces oxidation Impurity content in calcium, then obtained lime powder is added in supercritical carbon dioxide, supercritical CO2Expansion with gas The solvability of property and liquid is dissipated, while having both low-viscosity, the characteristic of low surface tension, supercritical CO2It can penetrate into rapidly Enter in CaO hole, since its viscosity is low and polarity is weak, reaction speed is greatly increased, while agglomeration greatly reduces, thus Realize that CaO is rapidly converted into calcium carbonate granule, while remaining supercritical CO2Fluid can penetrate into the hole of calcium carbonate granule Among, it then releases stress, then supercritical CO2Can be due to pressure reduction, the gasification of express delivery becomes carbon dioxide gas, then surpasses and face Boundary CO2Volume can expand in gasification, and according to measuring and calculating, in gasification, the expansion of volume reaches hundreds times, then permeate Supercritical CO among calcium carbonate granule hole2Expansion sharply, so that the separating twice of nano-calcium carbonate particles is realized, The degree of aggregation that further reduced nanometer calcium carbonate, according to experiment and detection data, in supercritical CO2Reaction obtains in fluid Nanometer calcium carbonate, degree of aggregation are generally 15-20, using supercritical CO2After the second-time breakage that the gasification of fluid is formed, reunite Degree is lower than 5, and the index for finally collecting obtained nanometer calcium carbonate is as follows:
The measurement method of degree of aggregation is that the primary particle size of nanometer calcium carbonate is measured by XRD, then passes through nanometer laser grain The partial size for the secondary agglomeration body that degree instrument measurement obtains, the ratio between partial size and primary particle size of secondary agglomeration body are degree of aggregation.
The present invention is by technical grade sulfuric acid calcium, dissolution and pyrolytic by ammonium hydrogen carbonate, then by calcining, realizes The purification of calcium, while also reducing cost;
In step 2, pass through supercritical CO2Fluid is as medium, carrier and reaction raw materials, by under supercriticality Special nature, while additional ultrasound substantially increases reaction efficiency, while decreasing the reunion of calcium carbonate, receives after reaction The degree of aggregation of rice calcium carbonate is generally 15-20, then releases stress, then due to the volume expansion of carbon dioxide, by nano-calcium carbonate Calcium carries out second-time breakage, and due to supercritical CO2It can penetrate among the hole of nanometer calcium carbonate, then this shattering process is high-efficient And effect is good, by this step, the degree of aggregation of final nanometer calcium carbonate be reduced to 5 hereinafter, and this process entirely without any pollution Object and waste water discharge, realize cleanly production, reaction process is simple, and at low cost.
The beneficial effects of the present invention are:
1. simple process and low cost, obtained nanometer calcium carbonate, good dispersion, reunion index is low, purity is high, impurity contains It measures low.
2. no waste water generates during calcium oxide is converted to nanometer calcium carbonate, also generated without other impurities ion, production High-efficient, environment-friendly type is good.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail, a kind of low agglomeration nano carbonic acid of the present embodiment The preparation method of calcium, is following steps:
(1) it pre-processes, water is added in calcium sulfate and carries out pulp, be then 15-35 DEG C of addition ammonium bicarbonate soln in temperature, It is 20-35 DEG C in temperature, pH is that 7.0-7.3 reacts 0.5-1 hours, then carries out secondary filter, filtrate, which is warming up to temperature, is It 80-90 DEG C, reacts 2-4 hours, then filters, air-flow after residue washing, drying is crushed, be then 650-750 DEG C in temperature Then calcining 1-2 hours crosses 300-350 mesh after air-flow is broken, obtains lime powder;
(2) lime powder for obtaining step (1) is added in the container equipped with supercritical carbon dioxide, and maintenance temperature is 45-55 DEG C, pressure is 75-80 atmospheric pressure, while then additional ultrasound, ultrasonic time 60-120min start to release stress, Container is connected to dust arrester installation simultaneously, collects solid to get low agglomeration nano calcium carbonate is arrived.
Calcium sulfate is technical grade purity in the step (1), and content of magnesium is lower than 100ppm, other metal impurities in calcium sulfate Content is lower than 50ppm, and granularity is less than 50 microns, and the mass ratio of calcium sulfate and water is 1:5-6 when pulp, ammonium bicarbonate soln it is dense Degree is 100-150g/L, and the molar ratio of the ammonium hydrogen carbonate of addition and calcium sulfate is 2.5-2.8:1, be added ammonium bicarbonate soln when Between be 1-2 hour, secondary filter uses ceramic filtration membrane, and the aperture of ceramic filtration membrane is 20-50nm.
The molar ratio of lime powder and supercritical carbon dioxide is 1:5-10 in the step (2), and ultrasonic power is 2-5kW, container inside lining polytetrafluoroethylene (PTFE) material, dust arrester installation include that two-stage is gathered dust, and the first order is cyclone dust collector, the second level For bagroom, for the cloth bag that bag collection uses for 1000-1200 mesh, cyclone dust collection material and bag collection material carry out mixing.
Container is connected to dust arrester installation by pipeline in the step (2), and ball valve is provided on pipeline, releases stress process For ball valve is opened.
Embodiment 1
A kind of preparation method of low agglomeration nano calcium carbonate, is following steps:
(1) it pre-processes, water is added in calcium sulfate and carries out pulp, be then 15-35 DEG C of addition ammonium bicarbonate soln in temperature, It is 25 DEG C in temperature, pH is 7.2 reaction 0.75 hour, then carries out secondary filter, and it is 85 DEG C that filtrate, which is warming up to temperature, reaction It 3.5 hours, then filters, air-flow after residue washing, drying is crushed, be then 695 DEG C of calcinings 1.5 hours in temperature, then 325 meshes are crossed after air-flow is broken, obtain lime powder;
(2) lime powder for obtaining step (1) is added in the container equipped with supercritical carbon dioxide, and maintenance temperature is 49.5 DEG C, pressure is 76.5 atmospheric pressure, while then additional ultrasound, ultrasonic time 70min start to release stress, and simultaneously will Container is connected to dust arrester installation, collects solid to get low agglomeration nano calcium carbonate is arrived.
Calcium sulfate is technical grade purity in the step (1), and content of magnesium is lower than 100ppm, other metal impurities in calcium sulfate Content is lower than 50ppm, and granularity is less than 50 microns, and the mass ratio of calcium sulfate and water is 1:5.2 when pulp, ammonium bicarbonate soln it is dense Degree is 125g/L, and the ammonium hydrogen carbonate of addition and the molar ratio of calcium sulfate are 2.65:1, and the time that ammonium bicarbonate soln is added is 1.5 Hour, secondary filter uses ceramic filtration membrane, and the aperture of ceramic filtration membrane is 35nm.
The molar ratio of lime powder and supercritical carbon dioxide is 1:8 in the step (2), and ultrasonic power is 3.5kW, container inside lining polytetrafluoroethylene (PTFE) material, dust arrester installation include that two-stage is gathered dust, and the first order is cyclone dust collector, the second level For bagroom, for the cloth bag that bag collection uses for 1000 mesh, cyclone dust collection material and bag collection material carry out mixing.
Container is connected to dust arrester installation by pipeline in the step (2), and ball valve is provided on pipeline, releases stress process For ball valve is opened.
The index for finally collecting obtained nanometer calcium carbonate is as follows:
Embodiment 2
A kind of preparation method of low agglomeration nano calcium carbonate, is following steps:
(1) it pre-processes, water is added in calcium sulfate and carries out pulp, be then 31 DEG C of addition ammonium bicarbonate solns, In in temperature Temperature is 31 DEG C, and pH is 7.15 reaction 0.6 hour, then carries out secondary filter, and it is 87 DEG C that filtrate, which is warming up to temperature, reaction It 3.5 hours, then filters, air-flow after residue washing, drying is crushed, be then 715 DEG C of calcinings 1.6 hours in temperature, then 300 meshes are crossed after air-flow is broken, obtain lime powder;
(2) lime powder for obtaining step (1) is added in the container equipped with supercritical carbon dioxide, and maintenance temperature is 49.5 DEG C, pressure is 76.5 atmospheric pressure, while then additional ultrasound, ultrasonic time 70min start to release stress, and simultaneously will Container is connected to dust arrester installation, collects solid to get low agglomeration nano calcium carbonate is arrived.
Calcium sulfate is technical grade purity in the step (1), and content of magnesium is lower than 100ppm, other metal impurities in calcium sulfate Content is lower than 50ppm, and granularity is less than 50 microns, and the mass ratio of calcium sulfate and water is 1:5.2 when pulp, ammonium bicarbonate soln it is dense Degree is 125g/L, and the ammonium hydrogen carbonate of addition and the molar ratio of calcium sulfate are 2.65:1, and the time that ammonium bicarbonate soln is added is 1.5 Hour, secondary filter uses ceramic filtration membrane, and the aperture of ceramic filtration membrane is 35nm.
The molar ratio of lime powder and supercritical carbon dioxide is 1:9.5 in the step (2), and ultrasonic power is 4.5kW, container inside lining polytetrafluoroethylene (PTFE) material, dust arrester installation include that two-stage is gathered dust, and the first order is cyclone dust collector, the second level For bagroom, for the cloth bag that bag collection uses for 1150 mesh, cyclone dust collection material and bag collection material carry out mixing.
Container is connected to dust arrester installation by pipeline in the step (2), and ball valve is provided on pipeline, releases stress process For ball valve is opened.
The index for finally collecting obtained nanometer calcium carbonate is as follows:
Index Ca Primary particle size D10 D50 D90
Numerical value 39.68% 13nm 19.5nm 50nm 68.5nm
D100 Fe Mg Na Ni Co
95.8nm 3ppm 11.9ppm 5.7ppm 3.8ppm 7.1ppm
Mn Zn Cu Ti Al Ba
8.7ppm 6.0ppm 4.7ppm 5.9ppm 5.9ppm 5.7ppm
Tap density Sulfate radical Chloride ion BET Degree of aggregation CaO
0.25g/mL 21.5ppm 5.9ppm 82.8m2/g 3.8 41.2ppm
Embodiment 3
A kind of preparation method of low agglomeration nano calcium carbonate, is following steps:
(1) it pre-processes, water is added in calcium sulfate and carries out pulp, be then 15-35 DEG C of addition ammonium bicarbonate soln in temperature, It is 30 DEG C in temperature, pH is 7.1 reaction 0.8 hour, then carries out secondary filter, and it is 87 DEG C that filtrate, which is warming up to temperature, reaction It 3.2 hours, then filters, air-flow after residue washing, drying is crushed, be then 720 DEG C of calcinings 1.5 hours in temperature, then 330 meshes are crossed after air-flow is broken, obtain lime powder;
(2) lime powder for obtaining step (1) is added in the container equipped with supercritical carbon dioxide, and maintenance temperature is 49 DEG C, pressure is 77 atmospheric pressure, while then additional ultrasound, ultrasonic time 68min start to release stress, while by container It is connected to dust arrester installation, collects solid to get low agglomeration nano calcium carbonate is arrived.
Calcium sulfate is technical grade purity in the step (1), and content of magnesium is lower than 100ppm, other metal impurities in calcium sulfate Content is lower than 50ppm, and granularity is less than 50 microns, and the mass ratio of calcium sulfate and water is 1:5.5 when pulp, ammonium bicarbonate soln it is dense Degree is 135g/L, and the ammonium hydrogen carbonate of addition and the molar ratio of calcium sulfate are 2.7:1, and the time that ammonium bicarbonate soln is added is 1.3 Hour, secondary filter uses ceramic filtration membrane, and the aperture of ceramic filtration membrane is 45nm.
The molar ratio of lime powder and supercritical carbon dioxide is 1:7 in the step (2), and ultrasonic power is 4kW, Container inside lining polytetrafluoroethylene (PTFE) material, dust arrester installation include that two-stage is gathered dust, and the first order is cyclone dust collector, and the second level is cloth bag Dust-precipitator, for the cloth bag that bag collection uses for 1200 mesh, cyclone dust collection material and bag collection material carry out mixing.
Container is connected to dust arrester installation by pipeline in the step (2), and ball valve is provided on pipeline, releases stress process For ball valve is opened.
The index for finally collecting obtained nanometer calcium carbonate is as follows:
Index Ca Primary particle size D10 D50 D90
Numerical value 39.65% 14nm 19nm 51nm 69nm
D100 Fe Mg Na Ni Co
85nm 1.5ppm 11.8ppm 6.8ppm 7.1ppm 6.4ppm
Mn Zn Cu Ti Al Ba
3.7ppm 2.1ppm 5.8ppm 1.8ppm 2.8ppm 1.7ppm
Tap density Sulfate radical Chloride ion BET Degree of aggregation CaO
0.22g/mL 21ppm 5ppm 83m2/g 3.6 43.8ppm
Embodiment 4
A kind of preparation method of low agglomeration nano calcium carbonate, is following steps:
(1) it pre-processes, water is added in calcium sulfate and carries out pulp, be then 18 DEG C of addition ammonium bicarbonate solns, In in temperature Temperature is 25 DEG C, and pH is 7.2 reaction 0.65 hour, then carries out secondary filter, and it is 85 DEG C that filtrate, which is warming up to temperature, reaction It 3.1 hours, then filters, air-flow after residue washing, drying is crushed, be then 690 DEG C of calcinings 1.5 hours in temperature, then 320 meshes are crossed after air-flow is broken, obtain lime powder;
(2) lime powder for obtaining step (1) is added in the container equipped with supercritical carbon dioxide, and maintenance temperature is 48 DEG C, pressure is 78 atmospheric pressure, while then additional ultrasound, ultrasonic time 75min start to release stress, while by container It is connected to dust arrester installation, collects solid to get low agglomeration nano calcium carbonate is arrived.
Calcium sulfate is technical grade purity in the step (1), and content of magnesium is lower than 100ppm, other metal impurities in calcium sulfate Content is lower than 50ppm, and granularity is less than 50 microns, and the mass ratio of calcium sulfate and water is 1:5.5 when pulp, ammonium bicarbonate soln it is dense Degree is 120g/L, and the ammonium hydrogen carbonate of addition and the molar ratio of calcium sulfate are 2.65:1, and the time that ammonium bicarbonate soln is added is 1.5 Hour, secondary filter uses ceramic filtration membrane, and the aperture of ceramic filtration membrane is 45nm.
The molar ratio of lime powder and supercritical carbon dioxide is 1:7.5 in the step (2), and ultrasonic power is 3.5kW, container inside lining polytetrafluoroethylene (PTFE) material, dust arrester installation include that two-stage is gathered dust, and the first order is cyclone dust collector, the second level For bagroom, for the cloth bag that bag collection uses for 1100 mesh, cyclone dust collection material and bag collection material carry out mixing.
Container is connected to dust arrester installation by pipeline in the step (2), and ball valve is provided on pipeline, releases stress process For ball valve is opened.
The index for finally collecting obtained nanometer calcium carbonate is as follows:
Index Ca Primary particle size D10 D50 D90
Numerical value 39.75% 11nm 15.7nm 48nm 68nm
D100 Fe Mg Na Ni Co
84nm 3.2ppm 10.8ppm 3.2ppm 4.2ppm 5.6ppm
Mn Zn Cu Ti Al Ba
4.1ppm 8.2ppm 4.1ppm 2.8ppm 5.7ppm 1.8ppm
Tap density Sulfate radical Chloride ion BET Degree of aggregation CaO
0.3g/mL 15.8ppm 5.7ppm 88m2/g 4.4 41.2ppm
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (4)

1. a kind of preparation method of low agglomeration nano calcium carbonate, which is characterized in that be following steps:
(1) it pre-processes, water is added in calcium sulfate and carries out pulp, be then 15-35 DEG C of addition ammonium bicarbonate soln in temperature, in temperature Degree is 20-35 DEG C, and pH is that 7.0-7.3 reacts 0.5-1 hours, then carries out secondary filter, and it is 80-90 that filtrate, which is warming up to temperature, DEG C, it reacts 2-4 hours, then filters, air-flow after residue washing, drying is crushed, be then 650-750 DEG C of calcining 1- in temperature 2 hours, 300-350 mesh then is crossed after air-flow is broken, obtains lime powder;
(2) lime powder for obtaining step (1) is added in the container equipped with supercritical carbon dioxide, and maintenance temperature is 45- 55 DEG C, pressure is 75-80 atmospheric pressure, while then additional ultrasound, ultrasonic time 60-120min start to release stress, simultaneously Container is connected to dust arrester installation, collects solid to get low agglomeration nano calcium carbonate is arrived.
2. a kind of preparation method of low agglomeration nano calcium carbonate according to claim 1, it is characterised in that: the step (1) calcium sulfate is technical grade purity in, and content of magnesium is lower than 100ppm in calcium sulfate, other metals content impurities are lower than 50ppm, grain Degree is less than 50 microns, and the mass ratio of calcium sulfate and water is 1:5-6 when pulp, and the concentration of ammonium bicarbonate soln is 100-150g/L, The ammonium hydrogen carbonate of addition and the molar ratio of calcium sulfate are 2.5-2.8:1, and the time that ammonium bicarbonate soln is added is 1-2 hours, essence Close filtering uses ceramic filtration membrane, and the aperture of ceramic filtration membrane is 20-50nm.
3. a kind of preparation method of low agglomeration nano calcium carbonate according to claim 1, it is characterised in that: the step (2) molar ratio of lime powder and supercritical carbon dioxide is 1:5-10 in, and ultrasonic power is 2-5kW, and container inside lining is poly- Tetrafluoroethene material, dust arrester installation include that two-stage is gathered dust, and the first order is cyclone dust collector, and the second level is bagroom, cloth Bag gathers dust the cloth bag used as 1000-1200 mesh, and cyclone dust collection material and bag collection material carry out mixing.
4. a kind of preparation method of low agglomeration nano calcium carbonate according to claim 1, it is characterised in that: the step (2) container is connected to dust arrester installation by pipeline in, and ball valve is provided on pipeline, and the process of releasing stress is to open ball valve.
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CN102491396B (en) * 2011-11-30 2014-08-06 厦门大学 Method for preparing nanometer calcium carbonate
CN102674424B (en) * 2012-04-28 2014-11-05 浙江大学 Method for preparing nanometer calcium carbonate slurry by using waste gypsum as calcium sources, products and application

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